JPH03500145A - Method for producing a plate-like support for a catalytic compound - Google Patents
Method for producing a plate-like support for a catalytic compoundInfo
- Publication number
- JPH03500145A JPH03500145A JP1505505A JP50550589A JPH03500145A JP H03500145 A JPH03500145 A JP H03500145A JP 1505505 A JP1505505 A JP 1505505A JP 50550589 A JP50550589 A JP 50550589A JP H03500145 A JPH03500145 A JP H03500145A
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- bath
- layer
- enamel
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003197 catalytic effect Effects 0.000 title claims description 30
- 150000001875 compounds Chemical class 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002002 slurry Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 210000003298 dental enamel Anatomy 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000021110 pickles Nutrition 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000004534 enameling Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 36
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 26
- 239000007789 gas Substances 0.000 description 10
- 230000009467 reduction Effects 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229940096529 carboxypolymethylene Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 150000002895 organic esters Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 241000287828 Gallus gallus Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 alkyl silicate Chemical compound 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- B01J35/56—
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 触媒作用化合物のプレート状担体の製造方法本発明は、完全な面又は格子状の、 成形された金属の基礎フレームを脱脂又は酸洗いした後、エナメル層を塗布して 、触媒作用化合物のプレート状の担体を製造する方法に関する。[Detailed description of the invention] Process for producing plate-like supports for catalytic compounds After degreasing or pickling the formed metal base frame, apply a layer of enamel. , relates to a method for producing plate-like supports of catalytic compounds.
触媒作用化合物のプレート状担体を製造するために、極めて様々な方法が公知で ある。連続的に、価格的に有利に製造する目的で、金属の基礎フレーム用の金属 薄板を金属のコイルから連続的に引き出し、帯の幅方向、従って搬送方向を横断 する方向に、一定のラスターでずらして配置した切り込みを入れ、帯の引き出し 方向、即ちンドメタル薄板へと立体的に変形し、このエキスノ（ンドメタル薄板 を脱脂することが既に提案された。次に、脱脂されたエキスバンドメタル薄板の 表面に更に、溶けた金属が噴射され、このように形成された粗い表面に触媒作用 物質が塗布された。次に葉状の保護層に挾んで、リブを構成するための圧縮成形 が、エキスバンドメタルの帯の搬送即ち引き出し方向に徐々に行われ、最後に、 保護層を除去した後、触媒作用化合物の施されたエキスノくンドメタル薄板は標 準の大きさに分割された（***国特許明細書第３２０８６３４号）。この種の触 媒プレートは、触媒担体の特別な構成に依存せずに価格的に有利に層を形成する という利点を提供する。触媒作用化合物のこのプレート状担体は特に廃棄ガスの 脱硝のための触媒プレートとして提案された。A wide variety of methods are known for producing plate-like supports for catalytic compounds. be. Metal for metal foundation frames for the purpose of continuous and cost-effective production. Thin sheets are drawn continuously from a metal coil, transversely across the width of the strip and therefore in the direction of conveyance. Make cuts that are staggered in a certain raster direction in the direction of the drawer. direction, that is, three-dimensionally deformed into a thin metal sheet. It has already been proposed to degrease the Next, the degreased expanded metal thin plate is Further molten metal is injected onto the surface, catalyzing the rough surface thus formed. substance was applied. Next, it is sandwiched between leaf-shaped protective layers and compression molded to form ribs. is carried out gradually in the direction of conveying or pulling out the strip of expanded metal, and finally, After removing the protective layer, the Exno-Kundo metal sheet with the catalytic compound is marked. (West German Patent Specification No. 3208634). This kind of touch The medium plate forms a layer at a cost advantage without depending on the special configuration of the catalyst support. provides the advantage of This plate-like carrier of catalytic compounds is especially suitable for waste gases. It was proposed as a catalyst plate for denitrification.
燃焼装置の廃棄ガスの脱硝の範囲では、金属担体の触媒作用表面が、廃棄ガス中 に含まれる不純物によって毒される危険が特別に顧慮されるべきである。これに 関する認識の示すところによれば、毒される危険は触媒毒の触媒作用表面への接 触の持続に伴って高くなる。触媒作用表面の担体を熱交換蓄熱体でなく回転式再 生熱交換器中に配設して、触媒作用化合物の担体に清浄な、例えば浄化されたガ スの気流と、浄化されるべきガスの気流とを交互にあてるようにすることが好ま しい。この時、この回転式再生熱交換用に開発され有効性が確認されている浄化 装置が、触媒作用表面に沈降した触媒毒を持続的に除去せしめる。しかしながら この種の浄化装置は同時に、浄化媒体、なかんずく空気又は加熱蒸気の噴流を触 媒作用表面に操作的にあてることにより、この表面に剥離の危険を伴う相当な負 荷を生ぜしめる。In the scope of denitrification of waste gases from combustion plants, the catalytically active surface of the metal carrier is Special consideration should be given to the risk of being poisoned by impurities contained in to this Knowledge on the subject indicates that the risk of poisoning is due to the contact of catalyst poisons with catalytic surfaces. The level increases as the touch continues. The catalytic surface support is a rotary recycler rather than a heat exchanger. The carrier of the catalytic compound is provided with clean, e.g. purified gas, in the bioheat exchanger. It is preferable to apply the airflow of the gas and the airflow of the gas to be purified alternately. Yes. At this time, a purification system developed for this rotary regenerative heat exchange and whose effectiveness has been confirmed. The device permanently removes catalyst poisons that have settled on the catalytic surfaces. however This type of purification device simultaneously uses a jet of purification medium, in particular air or heated steam. By operatively applying it to a mediating surface, this surface is subject to considerable stress with the risk of delamination. cause a burden.
本発明の基礎になっている課題は、特定の構成に依存せずにプレート状の担体に 触媒作用化合物の層をしつかり付着するように施し、特にその際、面全体に渡っ て一様な層を形成することである。The problem on which the invention is based is to Apply the layer of catalytic compound in a tightly adhering manner, especially over the entire surface. to form a uniform layer.
冒頭に述べた種類の方法から出発して、本発明による方法は、金属の基礎フレー ム上に、孔の少ない基層と耐酸性の高い粗い被覆層を形成するエナメルを塗布し て、これを基礎フレームの表面に基礎エナメルとして焼き付けること、更に、基 礎エナメルの層が形成された基礎フレームを、焼き付けに続いて先ず、運動を与 えられた触媒スラリー浴中に浸すことにより、触媒作用化合物の粉末、結合剤、 水、並びに場合によっては湿潤剤から成り剪断力の影響下で液化する触媒スラリ ーでぬらし、ぬらした基礎フレームを、スラリー浴の運動を維持したまま、再び 浴から引き離し、次いで乾燥部署へ送ることを特徴としている。この解決方法に より、運動を与えられ、剪断力の作用によって希釈溶液状をなしているスラリー 浴中に浸す間に、薄板又は格子は、例えば多層構造にするような特別な構成に依 存せずに、スラリーの粘稠度を選択することによって所望の層の厚さで、一様に ぬらされる。Starting from a method of the type mentioned at the outset, the method according to the invention is based on a metal basic frame. An enamel is applied on top of the film, forming a low-porosity base layer and a rough, acid-resistant covering layer. This is then baked onto the surface of the base frame as a base enamel. The base frame, on which the base enamel layer has been applied, is first subjected to movement following baking. The catalytic compound powder, binder, Catalyst slurry consisting of water and possibly a wetting agent that liquefies under the influence of shear forces Wet the base frame with It is characterized by being separated from the bath and then sent to the drying department. This solution Slurry that is given motion and forms a diluted solution due to the action of shearing force. During immersion in the bath, the lamella or grid may be subjected to a special construction, e.g. in a multi-layer structure. uniformly with the desired layer thickness by selecting the consistency of the slurry Getting wet.
スラリー浴中に浸すことでとりわけ、剪断力の作用の下で流動性を得た触媒スラ リーが、エナメルの粗い被覆層のくぼみの中にしみ込むことになり、これにより 、エナメルと触媒層の機械的に安定した結合状態が得られる。Catalytic slurry obtained, inter alia, becomes fluid under the action of shear forces by immersion in a slurry bath. This causes the lea to seep into the recesses of the rough covering layer of enamel, which causes , a mechanically stable bond between the enamel and the catalyst layer can be obtained.
薄板又は格子を浴から引き出す際にスラリーはエナメルを施された金属の担体の 表面で既に、特に０．５乃至２ｗｍの所望の層厚以内では重力の影響の下でプレ ート状担体の表面から流れ落ちることがもはやないところまで、固まっている。When the sheet or grid is withdrawn from the bath, the slurry is deposited on the enamelled metal carrier. Already at the surface, especially within the desired layer thickness of 0.5 to 2 wm, precipitates under the influence of gravity. It has solidified to the point that it can no longer run off the surface of the sheet-like carrier.
ここで触媒スラリーは、層形成による担体プレートの厚さの増加が面全体に渡っ て一定なままであるように、即ち例えばくぼみに触媒スラリーが詰められること のないように、担体プレートをぬらす。これにより担体プレートに１ ｍｉまで の層厚を具備させることが可能である。Here, the catalyst slurry has an increase in the thickness of the carrier plate due to layer formation over the entire surface. the catalyst slurry remains constant, i.e. the cavity is filled with catalyst slurry. Wet the carrier plate so that it is free of dirt. This allows the carrier plate to reach up to 1 mi. It is possible to have a layer thickness of .
エナメルの施された基礎フレームを下方へ導きながらスラリー浴中に浸し上方へ 導きながらスラリー浴から取り出す連続的なぬらし方、又は、スラリー浴を周期 的にもち上げ、次いでこれを降ろして、ぬらした担体を更に先へ搬送する非連続 なぬらし方は、何れも、個々の担体一つ一つに対して用いることもできるし、幾 つかの担体に同時に適用することも可能であり、幾つかの担体を筒状の架台の内 にまとめてぬらすことをも排除しない。剪断力の作用によって液化した触媒スラ リーを用いたこの種のぬらし方により、特に、エナメルを施した幾つかの基礎フ レームを筒状の架台内にまとめる場合にも、ぬらしている間に気体通路がふさが ることはないようになっている。かくして筒状の架台の内でぬらすぬらし方を、 層を改めて形成し直すという課題に用いることができる。While guiding the enamelled foundation frame downwards, it is immersed in the slurry bath and then upwards. Continuous wetting method where the slurry is removed from the bath while being guided, or the slurry bath is removed periodically. A discontinuous process in which the wetted carrier is transported further by lifting it up and then lowering it. Any method of wetting can be applied to each individual carrier, or it can be applied to any number of It is also possible to apply several carriers at the same time, and several carriers can be placed inside a cylindrical frame. It is not ruled out that they are wetted together. Catalyst slurry liquefied by shear force This type of wetting method with When the frames are assembled in a cylindrical frame, the gas passages may become blocked during wetting. It is designed to never happen. In this way, the method of wetting inside the cylindrical pedestal, It can be used for the task of re-forming a layer.
スラリー浴の運動は励振機を浴中に浸すことにより、又は攪拌機を浴中に入れる ことによって特に有利に達成することができる。これとは異なる構成によれば、 スラリー浴は一つ又は幾つかの容器壁から、間接的に運動を与えられる。このた めに例えばスラリー浴用の容器の底を励振機上に支持することが可能であり、又 は励振機をスラリー浴用の容器の被覆面に配設することも可能である。振動は電 気機械的に、又は空気式に、又は超音波によって励起されてもよいが、その際、 基礎エナメル層の形成された基礎フレームをぬらすためのスラリー浴中に定常波 が生じるのを避けて不規則な振動が生ぜしめられるようにする。Slurry bath motion can be achieved by submerging an exciter in the bath or by placing an agitator in the bath. This can be achieved particularly advantageously. According to a different configuration, The slurry bath is imparted with motion indirectly from one or several vessel walls. others For example, it is possible to support the bottom of a vessel for a slurry bath on an exciter; It is also possible to arrange the exciter on the coated surface of the container for the slurry bath. Vibration is electric It may be excited mechanically or pneumatically or by ultrasound; Standing waves in the slurry bath to wet the formed foundation frame with the foundation enamel layer To avoid the occurrence of irregular vibrations.
例えば炭化ケイ素のような発泡剤をエナメルフリットに添加すると、孔の少ない 基層及び粗い被覆層の形成が助けられる。孔の少ない基層が金属の基礎フレーム に対して係止する一方、エナメルを焼き付ける際に、発泡剤成分によって発生す る気泡により、粗い従って触媒スラリーを担持する能力のある被覆層が構成され る。エナメル層は、金属の担体と触媒作用化合物の層の間の熱的な調整層の機能 を、金属の基礎フレームの保護層の機能及び装着されるべき層のための付着層の 機能と結合させている。For example, adding a blowing agent, such as silicon carbide, to the enamel frit can help reduce porosity. Formation of the base layer and rough covering layer is aided. Base frame with metal base layer with few pores While it locks against The bubbles form a coarse coating layer that is capable of supporting the catalyst slurry. Ru. The enamel layer functions as a thermal conditioning layer between the metal support and the layer of catalytic compound. , the function of the protective layer of the metal base frame and the adhesion layer for the layer to be installed. It is combined with functionality.
剪断力の作用の下でのスラリー浴の液化は、例えばキサンタン（Ｘａｎｔｈａｎ ） 、カルボキシポリメチレンのようなチキソトロピー作用を有する添加物に よって助けることができる。剪断力の作用の下での触媒スラリーの液化の別の可 能性は、触媒作用化合物の粉末の製造に基づいて粒径の配分を選択することにあ る。このために粉末は、１０μｍよりも小さい粒径を持つものが１重量％以下、 ２００μｍより大きい粒径を持つものが５重量％以下であるような粒径の配分で 用いられる。触媒作用化合物の粉末の混合物中で粒径がより大きい場合には、場 合によってはスラリー製造に使用される液体を添加して挽くことにより、前記の 粒径の配分に合わせることができる。Liquefaction of a slurry bath under the action of shear forces can be achieved, for example, with xanthan (Xanthan). ), additives with thixotropic effects such as carboxypolymethylene So you can help. Another possibility of liquefaction of catalyst slurry under the action of shear forces is performance depends on selecting the particle size distribution based on the production of the powder of the catalytic compound. Ru. For this reason, the powder should contain 1% by weight or less of particles with a particle size smaller than 10 μm. Particle size distribution such that particles with a particle size larger than 200 μm account for 5% by weight or less. used. If the particle size is larger in the mixture of catalytic compound powders, In some cases, by grinding with the addition of liquid used for slurry production, the above-mentioned Can be adjusted to particle size distribution.
しっかり付着する層の装着のために特に有利なのは、湿潤剤を２％まで、スラリ ーの液化を引き起こす薬剤を５％まで添加し、更に水及び／又は結合剤を、層の 所望の厚さに対応したスラリー粘稠度になるまで添加することである。湿潤剤と しては例えば有機のエステル、結合剤としてはコロイドの二酸化ケイ素が適当で ある。Particularly advantageous for the application of well-adhering layers is the use of up to 2% wetting agent in the slurry. Add up to 5% of the agent that causes liquefaction of the layer and add water and/or binder to the layer. Add until a slurry consistency corresponding to the desired thickness is achieved. Wetting agent and For example, an organic ester is suitable as a binder, and colloidal silicon dioxide is suitable as a binder. be.
層を固くするのに有利なのは、触媒作用化合物でぬらし、エナメルを施した金属 の基礎フレーム上でこれを乾燥させた後燻焼することである。Advantageous for hardening the layer are metals wetted with catalytic compounds and enamelled. This is dried on a basic frame and then smoked.
更に、個体のブリッジを形成して層の強度を高めるのに有利なのは、層の形成さ れた担体にアルキルケイ酸塩又はその溶液を含浸させることである。このために 特に、場合によっては工業用アルコール、特にメタノールと混合されたテトラメ チルオルトケイ酸塩又はエチルポリケイ酸塩又はメチルポリケイ酸塩が考慮され る。Furthermore, it is advantageous to form solid bridges and increase the strength of the layer. This method involves impregnating a carrier with an alkyl silicate or its solution. For this In particular, tetramethane sometimes mixed with industrial alcohols, especially methanol. Chilorthosilicate or ethyl polysilicate or methyl polysilicate are considered Ru.
触媒作用化合物の層の形成されたプレート状の担体を連続的に製造するために、 特に有利であることが実証されているのは、先ずエナメルを施すのに適した鋼を コイルから引き出し、−列に成形し、標準の大きさに切り離し、更に次にこれら の標準部分を一列に脱脂又は酸洗いし、これらにエナメルを塗布して焼き付け、 次いでこれらの標準部分を、触媒スラリーの運動を与えられた浴の中でぬらし、 最後に焼き、場合によっては次いで燻焼することである。この種の層形成方法は 工業的に単純に実施可能である。触媒作用化合物の層を形成する前にプレート状 の担体を成形することにより、次に層の乾燥及び場合によっては燻焼を実施する ことができる。燻焼は熱的な後処理として、触媒作用化合物の乾燥が金属の担体 に与える侵食負荷が著しい場合にのみ、その後に続けて行われるべきである。For the continuous production of plate-like supports coated with layers of catalytic compounds, It has proven particularly advantageous to first obtain a suitable steel for enameling. Pulled from the coil, formed into rows, cut into standard sizes, and then Degrease or pickle standard parts in a row, apply enamel to them and bake them, These standard portions were then wetted in a bath given the motion of the catalyst slurry; The final step is grilling and, in some cases, smoking. This kind of layer formation method is It is industrially simple to implement. Plate-shaped before forming a layer of catalytic compound The layer is then dried and optionally smoldered by shaping the carrier. be able to. Smoking is a thermal post-treatment in which the catalytic compound is dried on a metal carrier. It should be followed only if the erosive loads on the surface are significant.
上に提案した触媒作用化合物のプレート状担体の製造方法によって、回転式再生 熱交換器に、−酸化炭素の酸化用にも酸化窒素の還元用にも触媒作用化合物の担 体を備えることができる。このために酸化窒素の還元用の触媒作用化合物の混合 物中又はその一部を成すスラリーの混合物中に、−酸化炭素の酸化用の触媒作用 化合物を含ませることも可能である。しかしながら一方で酸化窒素の還元、他方 で一酸化炭素の酸化の最適反応温度のレベルが異なるのに応じて、酸化窒素の還 元用の触媒作用層を高温ガス側に備え、場合によっては前を熱交換面で仕切って 、−酸化炭素の酸化用の層を低温ガス側に備えることが有利である。ここで高温 ガス側及び低温ガス側ということで、一つの触媒器内にまとめられる場合のみな らず、互いに切り離して配設された触媒器に分配される場合、例えば、ボイラー 装置のいわゆる高温端の、酸化窒素還元用のボイラーのすぐ後の回路にある触媒 器と、いわゆる低温端にある、従って例えば湿式脱硫部に直接付属しボイラー装 置の廃棄ガスの流れの内にある触媒器とに、分配される場合をも考えることがで きる。この種の解決方法によって、酸化窒素還元のための一時的な措置が、燃焼 側で廃棄ガス中の一酸化炭素の周囲への放出が高まることとひきかえに得られる という危険に対抗することができるが、この−酸化炭素の放出も同様に環境へ負 担をかけるものである。The above-proposed method for producing plate-like supports for catalytic compounds allows for rotary regeneration. The heat exchanger is loaded with catalytic compounds, both for the oxidation of carbon oxides and for the reduction of nitrogen oxides. You can prepare your body. For this purpose a mixture of catalytic compounds for the reduction of nitrogen oxides - catalytic action for the oxidation of carbon oxides in the slurry mixture forming or forming part of the product; It is also possible to include compounds. However, on the one hand, the reduction of nitrogen oxide; on the other hand, The reduction of nitrogen oxide depends on the level of optimal reaction temperature for the oxidation of carbon monoxide. The main catalytic layer is provided on the high-temperature gas side, and in some cases, the front is partitioned off with a heat exchange surface. , - It is advantageous to provide a layer for the oxidation of carbon oxides on the cold gas side. high temperature here Only when the gas side and low temperature gas side are combined in one catalytic converter. For example, in a boiler Catalyst in the circuit immediately after the boiler for nitrogen oxide reduction, at the so-called hot end of the device and boiler equipment located at the so-called cold end and therefore directly attached to the wet desulphurization section, for example. It is also possible to consider the case where the gas is distributed to a catalyst in the waste gas stream at the plant. Wear. This type of solution provides a temporary measure for nitrogen oxide reduction This is obtained in exchange for increased emissions of carbon monoxide in the waste gas into the surrounding environment. However, this release of carbon oxides is equally harmful to the environment. It is a burden.
燃焼装置の廃棄ガス中の酸化窒素の還元用の触媒器を形成するための、触媒作用 ゛化合物を備えたプレート状担体の製造を、以下の例でより詳細に説明する。Catalytic action to form a catalyst for the reduction of nitrogen oxides in the waste gas of combustion equipment The production of plate-like supports provided with compounds is explained in more detail in the following examples.
例 スプレーブースを通過する際エンドレスのコンベアに定置されて、担体プレート の形の金属の基礎フレームに、基礎エナメルフリットが塗布された。担体プレー トは次に予乾燥器により２００℃の温度で予乾燥され、次いで６乃至１０分間８ ２０℃の温度の焼き付は用オーブンを通過せしめられた。担体プレートは次に３ ０分以内の時−浴中に浸され、再び浴から引き離された。スラリー浴中で層の形 成された担体プレートは次に静止した周囲の空気の中で１０時間乾燥せしめられ た。スラリー溶用の長く延びた容器は長方形の底面を有しており、側壁に固定さ れた励振機を介して、担体プレートを浸している間、不規則な振動が容器中に生 ぜしめられた。example The carrier plate is placed on an endless conveyor as it passes through the spray booth. A basic enamel frit was applied to the metal basic frame in the form of . carrier play The material is then pre-dried in a pre-dryer at a temperature of 200°C and then dried for 6-10 minutes at 8°C. A baking oven at a temperature of 20° C. was passed. The carrier plate is then 3 Within 0 minutes - immersed in the bath and removed from the bath again. Layer shape in slurry bath The prepared carrier plate was then allowed to dry in still ambient air for 10 hours. Ta. The elongated vessel for slurry dissolution has a rectangular base and is fixed to the side wall. During the immersion of the carrier plate, irregular vibrations are generated in the container through an excited exciter. I was forced.
ここで触媒スラリー浴は、触媒作用化合物として遷移金属の酸化物、等に酸化バ ナジウム及び酸化タングステンが、結合剤としてコロイドの酸化ケイ素を持つ水 ガラスが配合された酸化チタンの粉末の混合物から成っていた。Here, the catalyst slurry bath contains oxides of transition metals, etc. as catalytic compounds. Nadium and tungsten oxide in water with colloidal silicon oxide as a binder It consisted of a mixture of titanium oxide powder mixed with glass.
摩耗抵抗を高めるためにスラリー浴は鉱物繊維を含んでいた。更にチキントロピ ー作用を持つ薬剤として、カルボキシポリメチレンと水との混合物が添加された 。最後にスラリー浴は湿潤剤として更に有機エステル（ツシメル・ラント・シュ ヴアルツ社（ｆｉｒ［［ｌａ Ｚｓｅｈｉｍｍｅｒ ＆Ｓｃｈｗａｒｚ ）の「 グリユードール（Ｇｌｙｄｏｌ） Ｊも含んでいた。The slurry bath contained mineral fibers to increase abrasion resistance. More chicken tropi – A mixture of carboxypolymethylene and water was added as an active agent. . Finally, the slurry bath is further treated with an organic ester (Tschmel-Land-Schmelt) as a wetting agent. Warz & Schwarz's " It also contained Glydol J.
上記の方法によって層の形成された担体プレートが、据え付けのテスト区間に取 り付けられた。溢流の長さは０．９ｍであった。この区間に褐炭を燃やすボイラ ーの廃棄ガス分流が、温度３４０＠、真空速度１２ｍ／秒で通された。この廃棄 ガス分流への還元剤（アンモニア）の添加は等モルに行われ、即ちボイラーの廃 棄ガス中に含まれる酸化窒素と添加されたアンモニアとの比はｌ：１であった。The carrier plate layered by the method described above is installed on the test section of the installation. attached. The length of the overflow was 0.9 m. A boiler that burns lignite in this section A waste gas stream of 100 ml was passed through at a temperature of 340 @ and a vacuum speed of 12 m/s. This disposal The addition of the reducing agent (ammonia) to the gas stream is equimolar, i.e. The ratio of nitrogen oxide contained in the waste gas to added ammonia was 1:1.
これらの条件の下で８２％の酸化窒素還元が達成された。Under these conditions 82% nitric oxide reduction was achieved.
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Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3821920.4 | 1988-06-29 | ||
| DE3821920A DE3821920A1 (en) | 1988-06-29 | 1988-06-29 | METHOD FOR PRODUCING A DISK-SHAPED CARRIER OF CATALYTICALLY ACTIVE CONNECTIONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03500145A true JPH03500145A (en) | 1991-01-17 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1505505A Pending JPH03500145A (en) | 1988-06-29 | 1989-05-26 | Method for producing a plate-like support for a catalytic compound |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4994430A (en) |
| EP (1) | EP0375759B1 (en) |
| JP (1) | JPH03500145A (en) |
| DE (2) | DE3821920A1 (en) |
| ES (1) | ES2013942A6 (en) |
| WO (1) | WO1990000089A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013233493A (en) * | 2012-05-08 | 2013-11-21 | Hitachi Zosen Corp | Method of manufacturing slurry for denitration catalyst and waste gas denitration device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19835662A1 (en) * | 1998-08-06 | 2000-02-17 | Siemens Ag | Production of a catalyst body used for purifying waste gas from e.g. waste incineration plants by applying enamel and a catalytically active material to a support and heat treating |
| EP1603723B2 (en) * | 2003-03-06 | 2018-06-27 | Vestas Wind Systems A/S | Pre-form and method of preparing a pre-form |
| US7326394B2 (en) * | 2003-03-07 | 2008-02-05 | Velocys | Catalysts, methods of making catalysts, and methods of combustion |
| US7874432B2 (en) | 2004-03-23 | 2011-01-25 | Velocys | Protected alloy surfaces in microchannel apparatus and catalysts, alumina supported catalysts, catalyst intermediates, and methods of forming catalysts and microchannel apparatus |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54138015A (en) * | 1978-04-19 | 1979-10-26 | Matsushita Electric Ind Co Ltd | Heat cooking utensile having selffcleaning coating layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| NL7400525A (en) * | 1973-01-27 | 1974-07-30 | ||
| JPS5428289A (en) * | 1977-08-05 | 1979-03-02 | Hitachi Ltd | Production of denitration catalys |
| DE3501330C1 (en) * | 1985-01-17 | 1986-01-23 | Kraftanlagen Ag, 6900 Heidelberg | Carrier matrix for taking up catalytically active compounds and method for producing the carrier matrix |
| DE3625474A1 (en) * | 1986-03-26 | 1988-02-04 | Kraftwerk Union Ag | PLATE-SHAPED CATALYST |
| DE3633515A1 (en) * | 1986-10-02 | 1988-04-14 | Didier Werke Ag | CATALYST IN THE FORM OF A PLATE FOR NITROGEN REDUCTION IN EXHAUST GAS |
-
1988
- 1988-06-29 DE DE3821920A patent/DE3821920A1/en active Granted
-
1989
- 1989-05-26 EP EP89906061A patent/EP0375759B1/en not_active Expired - Lifetime
- 1989-05-26 US US07/457,816 patent/US4994430A/en not_active Expired - Lifetime
- 1989-05-26 JP JP1505505A patent/JPH03500145A/en active Pending
- 1989-05-26 DE DE8989906061T patent/DE58901283D1/en not_active Expired - Fee Related
- 1989-05-26 WO PCT/EP1989/000586 patent/WO1990000089A1/en active IP Right Grant
- 1989-06-29 ES ES8902287A patent/ES2013942A6/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54138015A (en) * | 1978-04-19 | 1979-10-26 | Matsushita Electric Ind Co Ltd | Heat cooking utensile having selffcleaning coating layer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013233493A (en) * | 2012-05-08 | 2013-11-21 | Hitachi Zosen Corp | Method of manufacturing slurry for denitration catalyst and waste gas denitration device |
Also Published As
| Publication number | Publication date |
|---|---|
| US4994430A (en) | 1991-02-19 |
| DE58901283D1 (en) | 1992-06-04 |
| WO1990000089A1 (en) | 1990-01-11 |
| DE3821920A1 (en) | 1990-02-08 |
| EP0375759B1 (en) | 1992-04-29 |
| ES2013942A6 (en) | 1990-06-01 |
| EP0375759A1 (en) | 1990-07-04 |
| DE3821920C2 (en) | 1990-06-13 |
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